2-chloroethyl 3-oxobutanoate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 6-bromo-2-pyridine aldehyde (1.542 g, 8.29 mmol), chloroethyl acetoacetate (1.388 g, 8.43 mmol) and methyl 3-aminocrotonate (948 mg, 8.29 mmol) in 12 ml of isopropanol was stirred under a nitrogen gas stream, at 40° C. for 9 hours and at room temperature for 13 hours. The reaction solvent was distilled off under reduced pressure, and the residue was purified by column chromatography [silica gel; ethyl acetate-n-hexane (2:3)]. The crude product thus obtained was recrystallized from isopropyl ether-methanol to obtain 1.730 g (49% yield) of the above-captioned compound (m.p. 152° to 153°C.). at room temperature for 13 hours The reaction solvent was distilled off under reduced pressure the residue was purified by column chromatography [silica gel; ethyl acetate-n-hexane (2:3)] The crude product thus obtained was recrystallized from isopropyl ether-methanol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6-Cyano-2-pyridine aldehyde (1.613 g, 12.2 mmol), chloroethyl acetoacetate (2.009 g, 12.2 mmol) and methyl 3-aminocrotonate (1.364 g, 12.2 mmol) were dissolved in 16 ml of isopropanol, and the solution was stirred at 35° to 40° C. under a nitrogen gas stream for 14 hours. The reaction solvent was distilled off under reduced pressure, and the residue was purified by column chromatography [silica gel; ethyl acetate-n-hexane (5:6)]. The crude product thus obtained was recrystallized from isopropyl ether-methanol to obtain 1.546 g (34% yield) of the above-captioned compound. The reaction solvent was distilled off under reduced pressure the residue was purified by column chromatography [silica gel; ethyl acetate-n-hexane (5:6)] The crude product thus obtained was recrystallized from isopropyl ether-methanol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-nitrobenzaldehyde (4.536 g), 2-chloroethyl acetoacetate (4.94 g) and piperidine (110 mg) in benzene (18 ml) and acetic acid (360 mg) was refluxed for an hour under azeotropic dehydration. The reaction mixture was washed with water and dried. The solvent was distilled off to give an reddish oil of 2-chloroethyl 2-(2-nitrobenzylidene)acetoacetate, and thus obtained oil was treated with ethyl 3-amino-4,4-diethoxycrotonate (7.1 g) to give yellow granules of 2-chloroethyl 2-methyl-4-(2-nitrophenyl)-5-ethoxycarbonyl-6-diethoxymethyl-1,4-dihydropyridine-3-carboxylate, m.p. 82° to 84° C. (recrystallized from diisopropyl ether). was refluxed for an hour under azeotropic dehydration The reaction mixture was washed with water dried The solvent was distilled off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-nitrobenzaldehyde (4.536 g), 2-chloroethyl acetoacetate (4.94 g) and piperidine (110 mg) in benzene (18 ml) and acetic acid (360 mg) was refluxed for an hour under azeotropic dehydration. The reaction mixture was washed with water and dried. The solvent was distilled off to give an reddish oil of 2-chloroethyl 2-(2-nitrobenzylidene)acetoacetate, and thus obtained oil was treated with ethyl 3-amino-4,4-diethoxycrotonate (7.1 g) to give yellow granules of 2-chloroethyl 2-methyl-4-(2-nitrophenyl)-5-ethoxycarbonyl-6-diethoxymethyl-1,4-dihydropyridine-3-carboxylate, m.p. 82° to 84° C. (recrystallized from diisopropyl ether). was refluxed for an hour under azeotropic dehydration The reaction mixture was washed with water dried The solvent was distilled off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-nitrobenzaldehyde (4.536 g), 2-chloroethyl acetoacetate (4.94 g) and piperidine (110 mg) in benzene (18 ml) and acetic acid (360 mg) was refluxed for an hour under azeotropic dehydration. The reaction mixture was washed with water and dried. The solvent was distilled off to give an reddish oil of 2-chloroethyl 2-(2-nitrobenzylidene)acetoacetate, and thus obtained oil was treated with ethyl 3-amino-4,4-diethoxycrotonate (7.1 g) to give yellow granules of 2-chloroethyl 2-methyl-4-(2-nitrophenyl)- 5-ethoxycarbonyl-6-diethoxymethyl1,4 -dehydropyridine-3-carboxylate, m.p. 82° to 84° C. (recrystallized from diisopropyl ether). was refluxed for an hour under azeotropic dehydration The reaction mixture was washed with water dried The solvent was distilled off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 6-bromo-2-pyridine aldehyde (1.542 g, 8.29 mmol), chloroethyl acetoacetate (1.388 g, 8.43 mmol) and methyl 3-aminocrotonate (948 mg, 8.29 mmol) in 12 ml of isopropanol was stirred under a nitrogen gas stream, at 40° C. for 9 hours and at room temperature for 13 hours. The reaction solvent was distilled off under reduced pressure, and the residue was purified by column chromatography [silica gel; ethyl acetate-n-hexane (2:3)]. The crude product thus obtained was recrystallized from isopropyl ether-methanol to obtain 1.730 g (49% yield) of the above-captioned compound (m.p. 152° to 153°C.). at room temperature for 13 hours The reaction solvent was distilled off under reduced pressure the residue was purified by column chromatography [silica gel; ethyl acetate-n-hexane (2:3)] The crude product thus obtained was recrystallized from isopropyl ether-methanol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6-Cyano-2-pyridine aldehyde (1.613 g, 12.2 mmol), chloroethyl acetoacetate (2.009 g, 12.2 mmol) and methyl 3-aminocrotonate (1.364 g, 12.2 mmol) were dissolved in 16 ml of isopropanol, and the solution was stirred at 35° to 40° C. under a nitrogen gas stream for 14 hours. The reaction solvent was distilled off under reduced pressure, and the residue was purified by column chromatography [silica gel; ethyl acetate-n-hexane (5:6)]. The crude product thus obtained was recrystallized from isopropyl ether-methanol to obtain 1.546 g (34% yield) of the above-captioned compound. The reaction solvent was distilled off under reduced pressure the residue was purified by column chromatography [silica gel; ethyl acetate-n-hexane (5:6)] The crude product thus obtained was recrystallized from isopropyl ether-methanol

反応条件: temp:0.00; pressure:0.00; stir: